Matrix reactions of alkaline earth metal atoms with ozone

Thomas, Dwaine M.; Andrews, Lester

doi:10.1016/0022-2852(74)90230-6

Cited by 46 publications

(30 citation statements)

References 19 publications

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“…36 OCaO 2 and singlet CaO 3 at lower energy than triplet CaO 3 , the latter is clearly observed here. [4][5][6] Note that Ca + O 3is a true ozonide based on infrared, optical, and resonance Raman spectra. [4][5][6]37 Sr. Strontium follows calcium in the major difference between N 2 and Ar experiments with the same preference for group 6 bands in N 2 at the expense of group 1 bands.…”

Section: Discussionmentioning

confidence: 99%

“…[4][5][6] Note that Ca + O 3is a true ozonide based on infrared, optical, and resonance Raman spectra. [4][5][6]37 Sr. Strontium follows calcium in the major difference between N 2 and Ar experiments with the same preference for group 6 bands in N 2 at the expense of group 1 bands. Again near ultraviolet photolysis converted the cyclic SrO 2 species to the open (probably linear) OSrO molecule, and the ozonide SrO 3 increased on annealing.…”

Section: Discussionmentioning

confidence: 99%

“…2,7,8 Infrared spectra were recorded on a Nicolet 750 FTIR instrument at 0.5 cm -1 resolution. In addition complementary thermal experiments were done using Knudsen effusion [4][5][6] of Ca at 500 °C into condensing gas on a 12 ( 1 K substrate.…”

Section: Methodsmentioning

confidence: 99%

“…The use of a N 2 carrier gas increases the rate of the thermal Ca + O 2 reaction in the gas phase, 3 and CaO 2 product species can be formed in condensing nitrogen but not in condensing argon. [4][5][6] Recent infrared studies of pulsed laser evaporated alkaline-earth metal atoms and oxygen in argon have shown that the dioxide is the major product. 2 However, in preliminary nitrogen studies, calcium peroxide appears to be the major product formed, and a complete study of group 2 atom reactions with O 2 in nitrogen has been done in order to more fully characterize these peroxide molecular species.…”

Section: Introductionmentioning

confidence: 99%

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Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

et al. 1996

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Laser-ablated group 2 metal atoms have been reacted with O 2 in condensing N 2 to complement earlier Ar studies owing to different relaxation dynamics of N 2 and Ar with respect to excited metal atoms and ionic product molecules. In the case of Ca + O 2 , the reaction in condensing Ar gives primarily the 3 B 2 open bent OCaO dioxide product, but the reaction in condensing N 2 favors the 1 A 1 cyclic CaO 2 peroxide species. Three fundamentals are observed with 18 O and 44 Ca substitution for CaO 2 , and isotopic frequencies are in excellent agreement with the predictions of quantum chemical calculations. Although DFT/B3LYP frequencies are slightly higher than MP2 and CASSCF values, a similar pattern is calculated. Ionic molecules interact more strongly with a nitrogen matrix than with argon, and calculations of N 2 MO x and ArMO x molecules can be used to explain matrix shifts. Several N 2 MO 2 species are formed spontaneously from MO 2 molecules in solid nitrogen, and a match is found for observed matrix and DFT calculated isotopic frequencies. By comparison, the new molecule ArBeO 2 is identified in earlier argon matrix experiments. The new metal disuperoxide molecules, O 2 MO 2 , are also identified here. Calcium disuperoxide, O 2 CaO 2 , is characterized as a D 2d species with +1.12 charge on Ca and -0.28 on each O, in contrast to calcium peroxide, CaO 2 , a C 2V molecule with +1.05 charge on Ca and -0.525 on each oxygen atom.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

et al. 1996

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“…Reactions [ l ] and [6] show an 0,-to-NH, consumption ratio of 1.0. Reactions [7] and [8] are essentially a catalytic decomposition of 0 3 .…”

Section: Nh3-0 Reactionmentioning

confidence: 99%

Condensed-phase reactions of O₃ with NH₃ and NH₂OH

Huston¹,

Hisatsune²,

Heicklen³

1983

Can. J. Chem.

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The reactions of O3 with NH3 and NH2OH were studied in the condensed phase. A yellow ozonide was formed immediately upon the addition of O3 to the NH2OH solid maintained at −190 °C, but the yellow–orange ozonide seen in the NH3 case was not formed until the system was warmed to −170 °C. These ozonides could be reconverted to reactants by photolysis with near ultraviolet light or by heating to −90 °C (NH3+O3−) or −115 °C (NH2OH+O3−).Upon warming the NH3–O3 system to −130 °C, NH4NO3•3NH3 appeared. It started to deamminate at about −105 °C to give NH4NO3. In the NH3–O3 system a second species, tentatively identified as NH2O+HO2−, was also formed at −170 °C. It began to decompose with the evolution of O2 at about −10 °C.In the NH2OH–O3 system, HNO3 was also seen immediately upon addition of O3 to NH2OH. It appeared as NH2OH•HNO3, a hydrogen-bonded complex with NH2OH. At about −100 °C, NH2OH started to anneal and the NH2OH•HNO3 bands grew rapidly and converted to NH3OH+NO3−.There was no evidence of NH2OH as an intermediate in the NH3–O3 system, but since NH2OH reacted so readily with O3, this possibility could not be ruled out. These ozonolysis reactions may be represented as[Formula: see text]and[Formula: see text]

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Observation and Characterization of the Hg‐O Diatomic Molecule: A Matrix‐Isolation and Quantum‐Chemical Investigation

Andrews

Tsegaw

Cho

et al. 2022

Chemistry A European J

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Mercuric oxide is a well-known and stable solid, but the diatomic molecule HgÀ O is very fragile and does not survive detection in the gas phase. However, laser ablation of Hg atoms from a dental amalgam alloy target into argon or neon containing about 0.3 % of 16 O 2 or of 18 O 2 during their condensation into a cryogenic matrix at 4 K allows the formation of O atoms which react on annealing to make ozone and new IR absorptions in solid argon at 521.2 cm À 1 for Hg-16 O or at 496.4 cm À 1 for Hg-18 O with the oxygen isotopic frequency ratio 521.2/496.4 = 1.0499. Solid neon gives a 529.0 cm À 1 absorption with a small 7.8 cm À 1 blue shift. CCSD(T) calculations found 594 cm À 1 for Hg 16 O and 562 cm À 1 for Hg 18 O (frequency ratio = 1.0569). Such calculations usually produce harmonic frequencies that are slightly higher than the anharmonic (observed) values, which supports their relationship. These observed frequencies have the isotopic shift predicted for HgÀ O and are within the range of recent high-level frequency calculations for the HgÀ O molecule. Spectra for the related mercury superoxide and ozonide species are also considered for the first time.

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Matrix reactions of alkaline earth metal atoms with ozone

Cited by 46 publications

References 19 publications

Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

Condensed-phase reactions of O₃ with NH₃ and NH₂OH

Observation and Characterization of the Hg‐O Diatomic Molecule: A Matrix‐Isolation and Quantum‐Chemical Investigation

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Matrix reactions of alkaline earth metal atoms with ozone

Cited by 46 publications

References 19 publications

Infrared Spectra and Quantum Chemical Calculations of Group 2 MO2, O2MO2, and Related Molecules

Infrared Spectra and Quantum Chemical Calculations of Group 2 MO2, O2MO2, and Related Molecules

Condensed-phase reactions of O3 with NH3 and NH2OH

Observation and Characterization of the Hg‐O Diatomic Molecule: A Matrix‐Isolation and Quantum‐Chemical Investigation

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Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

Infrared Spectra and Quantum Chemical Calculations of Group 2 MO₂, O₂MO₂, and Related Molecules

Condensed-phase reactions of O₃ with NH₃ and NH₂OH